CHNG 1 CM BIN KH OXIT BN DN 1.1.

Gii thiu Cm bin kh oxit bn dn l loi cm bin kh n gin v c quan tm nht i vi nhng ng dng cm tay. Chng c nhng u im nh: kch thc gn, ch to n gin, gi thnh thp. Tuy nhin c mt s hn ch kh trnh khi v tnh chn lc v nhy nh c chn lc rng, p ng vi nhiu h kh khc nhau, n nh km. Tnh cht quan trng ca vt liu cm bin bn dn l s thay i tnh cht in khi tip xc vi kh cn d. Nguyn l d kh ca cm bin kh theo c ch b mt l s thay i tnh cht in ca vt liu khi t trong mi trng khng kh v mi trng c kh cn d. Nhng tng tc rn kh trn b mt nh hng ti mt in t, t lm thay i in tr ca vt liu. Hai c tnh quan trng ca cm bin kh l nhy v t l gia thi gian phn ng v thi gian phc hi ca cm bin. Vic pha tp kim loi hay oxit kim loi c th khc phc nhng nhc im ny. Cc oxit bn dn c ng dng trong cc thit b cm bin vi nhiu dng, trong mng mng l dng ph bin nht. Mng mng c th chia thnh hai nhm mng mng n tinh th v a tinh th. Mng mng n tinh th khng c s dng rng ri cho ng dng cm bin v in tr ca chng khng c kim sot bi bin ht v s thay i in tr l khng ng k khi tip xc vi kh. Trong khi , mng mng a tinh th rt ph hp cho ng dng nhy kh, bi v s trao i in tch qua bin ht l qu trnh ch yu kim sot in tr mng v chnh qu trnh ny chi phi c ch nhy kh ca cm bin. 1.2. nh ngha Cm bin l thit b nhn tn hiu hoc s kch thch t i tng v chuyn thnh tn hiu in [20]. Tn hiu u ra ca cm bin thng l tn hiu in. y l kt qu ca qu trnh x l tn hiu, ch dnh ring cho cc thit b in. Vi nh ngha ny, cm

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bin s chuyn i cc tn hiu c hc, tn hiu ha, tn hiu sinh hc thnh tn hiu in, a vo s dng vi cc mch in. Thit b cm bin l mt h phc tp bao gm: B cm bin, b x l tn hiu, b iu phi tn hiu, thit b nh v b khi ng. Tuy phc tp nhng cc thnh phn cu to c th c chia thnh 3 nhm khc nhau. u tin l b cm bin, th hai l b tip nhn tn hiu, th ba l b chuyn i tn hiu. Thnh phn th hai nhn tn hiu in ca b cm bin v tin hnh x l nh khuch i tn hiu, chuyn i thnh tn hiu s. Thnh phn th ba s chuyn i tn hiu s mt ln na ra tn hiu in, chuyn vo h o v hin th ln ca gi tr o trn mn hnh. 1.3. Cu to v nguyn tc hot ng 1.3.1. Cu to

Cu to n gin ca mt thit b cm bin kh bao gm mng oxit bn dn ph trn chu nhit c th l thy tinh hoc kim loi, hai in cc thu nhn tn hiu thay i in tr khi kh tip xc vi mng oxit bn dn (hnh 1.1).

Hnh 1.1: Cu to ca mt thit b cm bin kh. 1.3.2. Nguyn tc hot ng

Cm bin kh bn dn c th c chia thnh hai loi hot ng theo c ch khi v c ch b mt [20]. Trong trng hp u, tnh hp thc khi ca vt liu b thay i v s tng tc gia pha rn vi pha kh. Loi cm bin ny lm vic nhit cao. loi th hai, cm bin b mt bn dn, hin tng hp ph kh dn

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n s thay i dn b mt ca vt liu c s dng cho vic d kh. Khi khuch tn vo trong khi l khng cn thit m ch xy ra phn ng b mt, loi cm bin ny thng lm vic nhit thp hn cm bin khi. 1.3.2.1. C ch d kh khi S thay i v tnh dn khi ca oxit bn dn c th c s dng d kh (ch yu l Oxi). Nhng cm bin ny lm vic nhit cao (in hnh trn 600C) v s khuch tn cn nng lng hot ha cao. Trong trng hp kh Oxi, s khuch tn vo hay ra khi oxit lm thay i tnh hp thc ca Oxi trong khi bi phn ng Oxi ha kh. Oxi hp ph cn bng vi mt nt khuyt Oxi, y l c trng cho nhiu oxit bn dn loi n, nh SnO2-x, ZnO. Phng trnh cn bng c th c vit nh sau: Oo VO + O2 (g) + 2 e Hng s cn bng cho phn ng (1.1): K = [VO][ e] P(O2) Khi cn bng in tch: 2[VO] = [ e] Sau khi th (1.3) vo (1.2), ta thy: [ e] = (2K) P(O2)-1/6 (1.4) S m ca p sut ring phn Oxi c gi tr -1/6, c th thy rng s ph thuc ca p sut ring phn Oxi vo tng dn khi, ch yu l in t, hn l vo linh ng electron e : = F e (2K)1/3 P(O2)-1/6 (1.5) chn lc ca cm bin dn khi cao v d nhiu phn t c th hp ph b mt ca oxit, nhng ch c mt s khuch tn ng k vo khi. Nhng cm bin hot ng theo c ch khi d tm cc loi kh khc Oxi cng c th c gii thch tng t. Trong cc trng hp ny, phn ng Oxi ha kh nh dng phng trnh (1.1) phi c tnh ton chnh xc v qu trnh x l nhit ng lc kt thc c dng ly tha nh phng trnh (1.5). S dng vt liu nano tinh th cho cm bin dn khi c th ci thin ng k nhy v mt tng tc, s khuch tn (1.3) (1.2) (1.1)

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c tng cng bi cc bin ht. Tuy nhin, lc la c th thp hn v s khuch tn ca cc phn t khc cng c th c tng cng. Hn na, s ph thuc ca nng lng c trng cng b thay i trong mt s trng hp do sai hng tun hon. 1.3.2.2. C ch d kh b mt Nhng oxit bn dn nh ZnO, SnO2, WO3, c gia nhit trong khng kh khong 200C-300C c kh nng phn ng vi cc loi kh Oxi ha hoc kh kh dn n tnh cht in ca vt liu thay i. Nguyn nhn ca s thay i ny chnh l do s tng tc ca cc phn t kh vi b mt mng. Qu trnh d kh c m t nh sau: Hp ph v khuch tn nhng phn t kh trn b mt oxit bn dn, iu ny ph thuc nhit ca mi trng. Phn ng ca cc phn t kh d v cc phn t b hp ph ha hc trn b mt cm bin. Chnh s tng tc ny lm thay i tnh cht in ca vt liu, dn n thay i tn hiu nhn c ca thit b, trong trng hp oxit bn dn th l s chnh lch v in tr trc v sau khi tip xc vi kh d. Khi cc phn t kh d khuch tn vo lp b mt oxit bn dn, chng c xu hng bm cht ln b mt mng. Qu trnh ny c gi l s hp ph. S hp ph gm hai loi: hp ph vt l v hp ph ha hc. Vi hp ph vt l, cc nguyn t lin kt vi b mt ch bi lc lin kt yu (van der Waals). Hp ph ha hc l loi lin kt mnh gia cc nguyn t vi b mt oxit, loi lin kt ny s lm thay i cu trc ca b mt. Lin kt ha hc c th din ra i vi phn t hoc nguyn t. Hp ph ha hc thng xy ra sau qu trnh hp ph vt l khi c cung cp nng lng hot ha (thng thng l nhit nng). M hnh hp l ha trng thi ca cm bin trong mi trng o c xut bi Mark v nhng cng s [18] c m t nh sau:

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(1.6) Oxi hp ph trn b mt v rt electron t oxit bn dn to thnh O. S rt electron ny dn n vic hnh thnh vng ngho in tch gn b mt lm tng kh nng d kh ca cm bin (gi s bn dn loi n) hnh 1.2.

Hnh 1.2: Hnh nh ba chiu ca tinh th vt liu nhy kh sau khi hp th Oxi, vng nng lng gn b mt b un cong.

Hnh 1.3: M t chi tit vng nng lng un cong.

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Vi s c mt ca kh d chy nh Hyro, cht kh phn ng vi O v tr li electron cho bn dn, lm gim in tr. Lc ny xut hin s cnh tranh gia Oxi rt electron v kh chy tr li electron cho bn dn [37]. V nng Oxi trong mi trng o l hng s, nn iu kin n nh, gi tr in tr ph thuc vo nng ca kh chy. Nhng phn ng cnh tranh c minh ha nh sau:

(1.7) H2 gp mt cng nhiu, mt O cng gim dn n mt electron tng trong bn dn. V vy in tr ca mng bn dn thp. 1.4. Mt s c trng c bn ca cm bin kh 1.4.1. nhy

nhy c nh ngha l t l ca in tr ca mu o trong khng kh vi in tr trong mi trng c kh. * i vi kh kh, Ra > Rg nn nhy c tnh nh sau : S= Ra - Rg Ra (1.8)

Vi Ra l in tr trong khng kh (khi cha c kh d) Rg l in tr khi c kh d * i vi kh Oxi ha, Ra < Rg nn nhy c tnh nh sau :
S= Rg - Ra Ra

(1.9)

1.4.2.

Tnh lc la kh

Tnh lc la kh l mt c trng rt quan trng ca mt cm bin nhy theo c ch ha hc. Nh ta bit nhng cm bin kh c ch to t cc oxit kim loi th c kh nng nhy vi rt nhiu loi kh khc nhau (H2, CO, CH4, C3H8, C4H10, H2S, NO, NO2, ethanol, methanol, touluen, axeton). Nh vy vic ch to mt cm bin ch nhy vi mt loi kh no , cn i vi cc loi kh khc nhy khng ng k. iu ny rt c ngha ng dng trong i sng.

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Ngi ta thng dng cc cht xc tc thm vo nhm ci thin kh nng hot ng ca cm bin. Thm na, vi nguyn t xc tc thch hp s lm gim nhit hot ng ca cm bin vi kh cn d. Tnh chn lc thng c iu chnh bng cch thay i cc thng s cht pha tp, kch thc bin ht, cht xc tc, nhit hot ng, phng php ch to mng.

nhy

nhy

Hnh 1.4: nhy ca mng SnO2/Pt theo nhit i vi cc kh CO, CH4, C4H10, H2, C2H5OH. (a) Mng SnO2/Pt to bng phng php chm in t. (b) Mng SnO2/Pt to bng phng php phn x Magnetron phn ng. 1.4.3. Thi gian p ng/ Thi gian hi phc

Nhit (oC)

Thi gian p ng v thi gian hi phc l hai i lng rt quan trng xc nh tnh hiu qu ca cm bin. V nguyn tc cm bin c cho l c cht lng tt khi c thi gian p ng v thi gian hi phc ngn. Thi gian p ng l thi gian c tnh t lc cho kh vo n lc in tr gim n in tr p ng Rd. Thi gian p ng v Rd c tnh nh sau: khi cho

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kh th vo mng bt u gim in tr cho ti khi

R air -R d = 90% . Trong Rmax R max

l chnh lch in tr cc i, Rair l in tr mng ln nht khi cha c kh th. Thi gian hi phc l khong thi gian lc kh th gii hp ra khi mng n khi in tr hi phc n gi tr Rp. Thi gian hi phc v Rp c tnh nh sau: khi kh th c gii hp ra khi mng in tr mng phc hi ti gi tr sao cho
R p -R gas R max = 90% . Trong Rmax l chnh lch in tr cc i, Rgas l in tr

mng nh nht khi c kh th.

Hnh 1.5: S cho bit thi gian p ng thi/ gian hi phc ca cm bin kh. 1.5. Cc yu t nh hng n nhy kh 1.5.1. Nhit

Nhit ng vai tr quan trng trong qu trnh d kh ca cc cm bin bn dn do khng ch nh hng n tnh cht vt l ca bn dn m cn nh hng n tng tc trao i in t trn b mt mng. hiu r hn nh hng ny, ta xt s hp ph v chuyn ha Oxi, nc trn b mt mng. nhit phng, O2 c hp ph vt l ln b mt mng v ly in t trn mng chuyn thnh O2-. Khi tng nhit ln hn 150oC, O2- chuyn ha thnh 2O- hoc O2- tng ng vi vic bt mt hoc hai in t t mng, dn n s thay i cong vng nng lng v dn b mt. Cng ti nhit ny O2- cng bt u gii hp ra khi b mt mng, O- gii hp nhit ln hn 520oC. Nh vy, O- tn ti ch yu trong mng khong 150oC n 600oC, ng vai tr quan trng

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trong c ch nhy kh ca mng cn O2- khng bn do khng ng vai tr quyt nh nhy. Nc c th c hp ph di hai trng thi: phn t nc H2O (hp ph vt l) v nhng nhm hydroxyl OH- (hp ph ho hc). Phn t nc hp ph vt l trong khong 20oC n 160oC, d b gii hp ti 150oC, s hp ph ha hc H2O xy ra bi s hp ph OH- trn b mt mng din ra trong khong nhit t 200oC n 400oC v gii hp nhm OH- bt u 250oC, trong qu trnh gii hp s c s tr li in t cho mng lm cho in tr ca mng gim xung, nhm OH- gii hp cc i 500oC. Nh vy, m nh hng rt nhiu n tnh nhy kh ca cm bin to sai s cho php o, lm gim tin cy ca php o. Trong qu trnh o cn phi kim sot c m hoc phi c nh m trnh sai s.

Hnh 1.6: Cc thnh phn H2O hp ph nhit khc nhau c xc nh theo cc phng php o IR (php phn tch hng ngoi), TPD (phng php gii hp theo nhit ). 1.5.2. Cu trc mng xp cht v cu trc mng xp

Mng c hai loi cu trc khc nhau l cu trc xp cht v cu trc xp, ty vo tng loi cu trc mng m hnh thnh in tr khc nhau.

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Hnh 1.7: Cu trc mng xp v mng xp cht i vi mng xp cht, s thay i dn ch yu ch xy ra ti b mt, khi c th coi in tr ca b mt v in tr ca cu trc khi l hai in tr mc song song (hnh 1.8). Gi R1, R2 l cc tr b mt v tr khi tng ng. Do c s hp ph kh Oxi b mt nn R1 >> R2. Khi tng tr ca mng R12 s l : R1R2, R1 >> R2 R12 ~ R2 T phng trnh trn ta thy i vi mng b cht, tng tr ca mng t b chi phi bi in tr b mt R1. Ngha l, nhy ca mng rt km hoc s khng c tn hiu thay i [41]. i vi mt sensor nhy kh, thu c tn hiu mng c ph hai in cc, gia mng v in cc to ra mt in tr gi l in tr tip xc Rc (hnh 1.8). in tr ca mng sau khi ph in cc c xc nh: R = R12 + Rc = R2 + Rc. (1.10) V vy i vi mng c cu trc xp cht, s tip xc gia in cc vi mng rt quan trng, l mt yu t khng th b qua khi ch to cm bin.

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Hnh 1.8: S minh ha cu trc mng xp cht. in tr o c s c gi tr R = Rc+R12 Rc+R2 vi Rc l in tr tip xc. i vi mng c cu trc xp th trong vi cu trc mng c cc bin ht v gia cc bin ht s tn ti cc in tr Rgi. in tr Rgi ny c sinh ra do qu trnh hp ph kh Oxi v to nn cc vng ngho gia cc bin ht (hnh 1.9). Khi tng tr ca mng s l tng ca cc in tr Rgi ni tip nhau [41]. Rnt = Rgi (1.11)

Hnh 1.9: S hnh thnh in tr ca mng c cu trc xp in tr ca mng c cu trc xp sau khi ph in cc:

R = R c + R gi
V R gi >> R c R = R gi Vi Rc: L in tr ca in cc.

(1.12) (1.13)

T phng trnh (1.13) cho thy, trong cu trc xp, c th b qua in tr tip xc ca in cc vi mng. So snh (1.10) v (1.13) cho thy, in tr ca mng c cu trc xp c in tr ln hn nhiu so vi mng c cu trc xp cht. in tr ca cu trc xp rt ln lm cho s thay i in tr trc v sau khi c kh d thay i ng k. Do nhy ca mng cao hn so vi mng c cu trc xp cht. y chnh l u im ni bt ca phng php solgel dng to mng c cu trc xp ng dng lm mng nhy kh.

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1.5.3.

Kch thc ht

Mt trong nhng nhn t quan trng nht nh hng n tnh nhy kh l kch thc ht. Theo cc nghin cu c hai hiu ng ca kch thc ht nh hng n b mt ca mng. Theo hiu ng hnh hc, i vi cm bin lm dng mng mng, vic tng t s (S/V) ng ngha vi vic gim kch thc ht. Khi kch thc ht gim, din tch tip xc b mt tng v nhy cm bin tng. Theo hiu ng vt l, nh ta bit ro th nng gia cc bin ht ph thuc vo kch thc ht v ng thi n cng nh hng n dn ca mng. Cho nn khi kch thc ht ca vt liu lm cm bin thay i, nhy ca cm bin cng thay i. lm r vn ny ta c th biu din qua phng trnh Arrchenius [21].

- eVs = 0 exp k bT

(1.14)

trong 0 l h s dn khi, kB l hng s Boltzmann, T l nhit hp ph v eVs l ro th nng gia hai ht k nhau. Ro th nng c biu din theo hai cng thc sau.

e NDW2 eVs = 2
2 e2 Ns eVs = 2N D

(1.15)

(1.16)

trong W l rng ro th Schottky ( rng vng ngho), eVS l chiu cao ro th, l hng s in mi, ND l mt cc mc donor, l hng s in mi, NS l mt trng thi ca cc ion Oxi b hp ph trn b mt. T phng trnh 1.14, 1.15, 1.16 ta thy , eVs, Ns v W c mi lin h vi nhau. Trong W li ph thuc vo kch thc ht, nn khi kch thc ht nh, W ln, eVs tng ln dn n nhy tng.

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1.5.4.

S pha tp vai tr ca cht xc tc

Mc ch pha tp l kim sot tnh cht b mt ca mng oxit bn dn nhm tng nhy v gim nhit hot ng ca cm bin kh. ng thi, nhng cht thm vo ny cn c tc dng tng tnh chn lc cho u d. nh hng ca cht pha tp ln tnh chn lc ca cm bin bn dn vi vt liu nn l SnO2 c cho bi bng sau: Bng 1.1: nh hng ca cht pha tp ln tnh d kh ca vt liu SnO2. Cht pha tp CaO CeO2 La2O3 Pd Pt ThO2 Kim loi thuc nhm III (Ga. Al. In) Bi2O3 Os Cd Rh Au Ag Kh cn d Kh c mi CH4 CO2 CO, CH4 CO CO, C3H9N NxOy CO CH4 EtOH. H2 C2H4O CO H2, H2S, C3H8

nhy ca cc thit b cm bin bn dn ph thuc ch yu vo dn ca oxit kim loi ng vi mi trng khng kh xung quanh. Tuy nhin trong khng kh l mt hn hp kh cng tn ti, do i hi cc thit b cm bin phi c chn lc, nhy cao, thi gian phn ng v nhit phn ng thp. iu ny c ci thin bng cch pha tp thm mt lng kim loi vo cht nn. Vi mt lng nh cc kim loi xc tc nh Pd v Pt, hoc l Au v Li s ci thin rt nhiu tnh nhy ca mng cm bin. Ngoi ra, s hin din ca cht pha tp cng gp phn lm

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gim kch thc ht. Nghin cu cho thy bng cch pha tp thm Pt v Pd vo bt nano SnO2 s thay i theo chiu hng gim ca s pht trin v mt ng hc rt nhiu, pha tp nng cao, s thu c ht c kch thc nh.

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